Versatile Synthesis of Amine-Reactive Microgels by Self-Assembly of Azlactone-Containing Block Copolymers
Abstract
Relations between molecular design, chemical functionality, and stimulus-triggered response are important for a variety of applications of polymeric systems. In this paper, reactive amphiphilic block copolymers (BCPs) of poly(2-vinylpyridine)-block-poly(2-vinyl-4,4-dimethylazlactone) (PVP-b-PVDMA) were synthesized and assembled into microgels capable of incorporating functional amines. The composition of the PVP-b-PVDMA BCPs was varied to control the number of reactive sites in the spherical aggregates created by self-assembly of PVP-b-PVDMA BCPs in a 2-propanol/THF (v:v = 19:1) solvent mixture, which is selective for PVP. PVDMA and PVP segments were selectively cross-linked by 1,4-diaminobutane (DAB) or 1,4-diiodobutane (DIB) to fabricate core- and corona-cross-linked azlactone-containing microgels, respectively. Non-cross-linked aggregates of PVP-b-PVDMA and DIB-cross-linked microgels dissociate when exposed to THF, which is a good solvent for both blocks. However, the DAB-cross-linked BCP microgels swell in THF, suggesting the formation of a stable, three-dimensional network structure. Finally, because of their ability to be reactively modified in ways that allows their stability or disassembly characteristics to be tailored, these azlactone-containing BCP microgels provide an attractive platform for applications in a wide range of fields, including catalysis, imaging, molecule separation, and guest loading for targeted delivery.
- Authors:
-
[1];
[2];
[3];
[4]
- Shandong Univ., Jinan (China). National Engineering Research Center for Colloidal Materials. School of Chemistry and Chemical Engineering; Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry
- Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences
- Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry. Dept. of Chemical and Biomolecular Engineering
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States); Shandong Univ., Jinan (China)
- Sponsoring Org.:
- USDOE Office of Science (SC); National Science Foundation (NSF); Program of Qilu Young Scholars of Shandong Univ. (China); National Natural Science Foundation of China (NNSFC)
- OSTI Identifier:
- 1468208
- Grant/Contract Number:
- AC05-00OR22725; 1131252; 1512221; 21704057
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Macromolecules
- Additional Journal Information:
- Journal Volume: 51; Journal Issue: 10; Journal ID: ISSN 0024-9297
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Wang, Xu, Davis, Jesse L., Aden, Bethany M., Lokitz, Bradley S., and Kilbey, S. Michael. Versatile Synthesis of Amine-Reactive Microgels by Self-Assembly of Azlactone-Containing Block Copolymers. United States: N. p., 2018.
Web. doi:10.1021/acs.macromol.8b00405.
Wang, Xu, Davis, Jesse L., Aden, Bethany M., Lokitz, Bradley S., & Kilbey, S. Michael. Versatile Synthesis of Amine-Reactive Microgels by Self-Assembly of Azlactone-Containing Block Copolymers. United States. https://doi.org/10.1021/acs.macromol.8b00405
Wang, Xu, Davis, Jesse L., Aden, Bethany M., Lokitz, Bradley S., and Kilbey, S. Michael. Fri .
"Versatile Synthesis of Amine-Reactive Microgels by Self-Assembly of Azlactone-Containing Block Copolymers". United States. https://doi.org/10.1021/acs.macromol.8b00405. https://www.osti.gov/servlets/purl/1468208.
@article{osti_1468208,
title = {Versatile Synthesis of Amine-Reactive Microgels by Self-Assembly of Azlactone-Containing Block Copolymers},
author = {Wang, Xu and Davis, Jesse L. and Aden, Bethany M. and Lokitz, Bradley S. and Kilbey, S. Michael},
abstractNote = {Relations between molecular design, chemical functionality, and stimulus-triggered response are important for a variety of applications of polymeric systems. In this paper, reactive amphiphilic block copolymers (BCPs) of poly(2-vinylpyridine)-block-poly(2-vinyl-4,4-dimethylazlactone) (PVP-b-PVDMA) were synthesized and assembled into microgels capable of incorporating functional amines. The composition of the PVP-b-PVDMA BCPs was varied to control the number of reactive sites in the spherical aggregates created by self-assembly of PVP-b-PVDMA BCPs in a 2-propanol/THF (v:v = 19:1) solvent mixture, which is selective for PVP. PVDMA and PVP segments were selectively cross-linked by 1,4-diaminobutane (DAB) or 1,4-diiodobutane (DIB) to fabricate core- and corona-cross-linked azlactone-containing microgels, respectively. Non-cross-linked aggregates of PVP-b-PVDMA and DIB-cross-linked microgels dissociate when exposed to THF, which is a good solvent for both blocks. However, the DAB-cross-linked BCP microgels swell in THF, suggesting the formation of a stable, three-dimensional network structure. Finally, because of their ability to be reactively modified in ways that allows their stability or disassembly characteristics to be tailored, these azlactone-containing BCP microgels provide an attractive platform for applications in a wide range of fields, including catalysis, imaging, molecule separation, and guest loading for targeted delivery.},
doi = {10.1021/acs.macromol.8b00405},
journal = {Macromolecules},
number = 10,
volume = 51,
place = {United States},
year = {2018},
month = {5}
}
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Works referencing / citing this record:
Recent Advances in Azlactone Transformations: Recent Advances in Azlactone Transformations
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